The solid-state mechanochemical method was proved to be a fast, simple, and efficient route to the synthesis of heterometallic [Au(CN)(2)]-based coordination polymers. Thus, a series of mixed-metal complexes, such as KCo[Au(CN)(2)](3), KNi[Au(CN)(2)](3), Cu(H2O)(2)[Au(CN)(2)](2), and Zn[Au(CN)(2)](2), was obtained by grinding stoichiometric amounts of K[Au(CN)(2)] and transition metal(II) chlorides. This solid-state method rapidly yields pure dicyanoaurate-based compounds, also in cases when the aqueous solution synthesis leads to an unseparable mixture of products. In addition, in some cases, the solid state reaction was faster than the corresponding solvent-based reaction. This mechanochemical method can be applied also to main group metals to obtain various cyanoaurate-based heterometallic coordination polymers, such as Me2Sn[Au(CN)(2)](2). and Ph3Sn[Au(CN)(2)]. For the 2:1 mixture of K[Au(CN)(2)] and Me2SnCl2, the dramatic enhancement of the reaction rate by the presence of a minor amount of water was noticed. In Ph3Sn[Au(CN)(2)], as was revealed by single-crystal X-ray diffraction, each Ph3Sn unit is linked to two others by two Au(CN)(2) bridges via Sn-N bonds to form an infinite cyanide-bridged chain. There are no Au center dot center dot center dot Au contacts between the chains due to the sterical hindrance of the phenyl groups. A dehydrated blue Co[Au(CN)(2)](2) complex was obtained during grinding or heating of the moderate-pink Co(H2O)(2)[Au(CN)(2)](2) complex. This complex displays a vapochromic response when exposed to a variety of organic solvents, as well as water and ammonia vapors.